Process of dyeing textile fibers



Patented Apr. 7, 1931 UNITED", STATES PATENT OFFICE I JEAN GEORGES KERN, OF WALTHAM, MASSACHUSETTS, AND CHARLES J. SALA, OF WILMINGTON, DELAWARE, ASSIGNORS T0 E. I. DU PONT DE NEMOUBS &; COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE PROCESS OF DYEING TEXTILE FIBERS No Drawing. Original application filed August 4, 1927, Serial No. 210,714. Divided and this application filed March 21, 1930. Serial No. 437,935.

This case is a division of our copending applicyition Serial No. 210,714, filed August 4 192 This invention relates to alkylolamine salts of aliphatic acids both saturated and unsaturated and to the sulfonic acid derivatives of these acids and niore particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamines, by combination with the fatty acids mentioned above by any of the well known methods for the production of sa ts.

The bases used for our purpose may be represented by the following general formula:

where Alk represents an aliphatic or hydroxy aliphatic radical R and R represent hydrogen or an aliphatic radical or a hydroxy aliphatic radical or a poly hydroxyvaliphatic radical. In making these new soluble oils we may proceed as follows The free fatty acids are combined directly with an organic base or a mixture of such bases. If the fatty acid is a solid the preparation is aided by the application of heat. It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil, caster oil, linseed oil and the like by saponifying the glycerides by heating with the base to a high temperature. we find that the reactionis complete when a sample of the mixture dissolves entirely in water. If water is present at the start this may be driven off, the base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is neces- 88.1%]110 give the most satisfactory results.

en preparing the products obtained In this case from the sulfonated fattyacids we may proceed as follows:

The acid product of the mixture of the sulfonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is free of mineral acid by washing. It is then freed of water either by settling or by any other-suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups. The following examples will serve to illustrate our method of procedure, but it is to be understood that the invention is not to be limited thereby:

Example 1 2823. '7 parts of free oleic acid are mixed with 1490 parts of tri-ethanolamine I Emam/ple 2 parts of oleic acid are mixed with The resultantproduct is' a clear yellow oil, I i

very soluble in water.

' Example 4 372 parts castor oil are mixed with 260 parts tri-ethanolamine 200 parts water The above mixture is heated on the water tri-ethanolamine, above the quantity mentioned.

E wample 5 284. 39 pargs ofdstearic acid are melted. Into the melt are s mm 149 parts tri-ethanolamine,stirring is continued at a tem etature of about 80 C. until the mixture is uni orm The resultant product on cooling is a solid,

not very soluble in water but very soluble in alcohol. It acts as an excellent assistant in promoting solution.

Example 6 282 parts oleic acid 91 parts of amino-propane diol NH CH CHCH 0H are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15 to 20%.

Example '7 282 parts oleic acid are caused to react as given in the above example with 119 parts of methyl di-ethanolamine CH3-N= (CH2-CH2OH)2 The soap obtained in this way has the property, when in alcoholic solution, of d1ssolvmg mercuric oxide and giving a relatlvely stable product soluble in water. This 1s altogether a surprising result and lllustrates the use'of these new soaps for pharmaceutr cal purposes.

E wample 8 6 parts of a crude sulfonatcd oil made by the action of sulfuric acid on castor oil are mixed with 1 part of mono-ethanolamine Example 9 2. 7 parts of a crude sulfonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand triethanolamine The products of Examples 8 and 9 are entirely soluble in water. They are thick yellow oils presumably containing salts of the bases of the sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purposes.

In dyeingPonsol Blue GD Double Paste, Schultz No. 842, on cotton yarn in the pack age machine, using 5% of color, 2 sodium hydroxide, 3% hydrosulfite, the addition of 1% of the product formed by combining 1 mole of sulfo-ricinoleic acid and 1 mole triethanolamine, containing di-ethanolamine, results in a brighter, more level dyeing.

The use in dyeing of the new compounds described in this case can be illustrated by the following example:

Example 10 An 8.5 dyeingof Ponsol Blue GD, Schultz No 842, on 150 pounds of mercerized cotton piece goods is obtained as follows:

12.75 pounds Ponsol Blue GD, Schultz No. 842, are mixed with 8.16 pounds of one of the compounds described in the examples of this case; 1 gallon of cold water is added and the suspension passed through a fine screen. A perfect speckless paste is thus obtained, which is added to the jigger dye bath composed of the following:

10 pounds caustic soda 15 pounds hydrosulfite concentrated. 10 pounds being added immediately and 5 pounds being added after one passage of the goods 100 gallons of water The temperature is raised to 110 F., and after complete reduction the dyeing started at this temperature. The temperature is then allowed to rise during 30 minutes to 125 G, and further dyed at this temperature for 10 to 15 minutes. Then give 1 wash, 4. passages in sodium perborate, 2 lbs. per 100 gals. at 120 F 2 cold washes, 5 passes in boiling soap solution 3 lbs. soap to 100 gallons, then rinse and wash in the open, dry and calender. This example, illustrating the method of dyeing, is similar to Example 1 given in copending application Serial No. 210,715, filed by applicants on August 4 1927. The difference between this example and the said Example 1 lies in the substitution of the novel assistants herein disclosed by applicants.

E mample 11 The new compounds described in this application may be used as assistants in the making of vat color pastes in a manner similar to the pastes described in applicants patented application bearing Patent Number 1,705,118, granted l\1arch 19, 1929. The dyestuif paste, as produced in the course of manufacture of Ponsol Blue GD, Schultz No. 842, is converted into a press cake containing 30% of dry color. 400 parts of the press cake are then mixed with 20 parts of glycerine and 580 parts of one of the assistants prepared according to Examples 1 to 9 and Example 18 of this application. It is possible to vary the quantities considerably without losin the advantages of this invention.

Example 12 The new compounds described in this case may be used in printing pastes containing lakes of basic colors. The mode of procedure in using such a printing paste is illustrated in the following example:

10 parts basic color (suitable for discharge printing) 50 parts glycerine 50 parts of any one of the products described in Examples 1 to 9 and Example 13 of this application 250 parts water 580 parts thickening composed of starch or gums and a certain amount of sodium hydrosulfite formaldeliyde necessary to cut the ground 60 parts tannin dissolved in equal parts of water or alcohol The textile or other material printed with this composition is aged and heated, passed into antimony salts, washed, and finished as usual. The process of printing illustrated in this example is identical with Example 4 in applicants co-pending case Serial No. 195,579, filed May 31, 1927, except for the insertion of the new assistants which comprise part of applicants herein disclosed invention.

. Example '13 Ha pure product is needed the operation maybe carried out as follows:

378 parts of pure sulfo-ricinoleic acid prepared by the action of chloro-sulfonic acid on pure ricinoleic acid are mixed with 149 parts of tri-ethanolamine In the above case the addition of a further molecular equivalent of base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determined.

In the above examples any one of the bases as defined by the general formula given above may be used either alone or in mixture. The fatty acids may also be varied through a wide range.

. By the term alkylol, as used herein, We mean to include an alkyl radical in which one or more hydrogens are replaced by a hydroxyl group, and may be represented by the fol lowing:

GnH2n-OH CnHZn-l 2- We have found that these products, which are essentially organic soaps possess a greater dissolvm power or dispersing power for 'organic su stances than do ordinary soaps.

They possess the detergent property of soaps without the high alkalinity characteristic of sodium or otassium salts of the fatty acids.

These pro ucts for these reasons have a distinct advantage for many purposes and particularly as assistants in dyeing, and those compounds which are derived from sulfonated castor oil by the process mentioned are in"many ways superior to ordinary sulfonated oils. Their superiority is evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brilliance of the dyeing.

When added to water the brin about solution or dispersion in so ne a orm as to appear a'solution of insoluble organic bases such as amino-azo-benzene, para-nitro-benindicates their probable value in pharma-- .cology, for example, in the production of antiseptic soaps and the like.

As many apparently widely difi'erent embodiments of this invention may be made without departing from the s irit thereof, it is to be understood that we 0 not intend to limit ourselves to the specific embodiments thereofexcept as indicated in the appended claims.

We claim:

1. In a process of applying a dye to tex- I tile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of oleic acid and an alkylolamine.

2. In a process of applying a dye to textile fibers, the step which comprises mixing with fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of oleic acid and at least one of the substances from the group consisting of di-ethanolamine and tri-ethanolamine.

5. In a process of applying a dye to textile fibers the step which comprises mixing with said dye a product resulting from the chemical combination of oleic acid and tri-ethanolamine.

6. In a process of applying a dye to textile fibers, the step which comprlses mixing with said dye a product resultin from the chemical combination of oleic aci and a compound having the following formula:

represent a monovalent substance from the group consisting of hydrogen, aliphatic radizene, azo-diphenylamine, benzene-azo-naph- I cals hydroxy aliphatic radicals and polyhY' droxy aliphatic radicals.

7 In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of oleic acid and a mixture of diand tri-ethanolamines.

8. a process of applying a dye to textile fibers, the step which comprises mixing with said' dyea product resulting from the chemical Icombination of oleic acid and di-ethanolamine.

9. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of oleic acid and mono-ethanolamine.

In testimony whereof, We afiix our signatures.

JEAN GEORGES KERN. CHARLES J. SALA. 

